2-thiaphosphono compounds



United States Patent 3,235,628 Z-THIAPHOSPHONO COMPOUNDS George M.Calhoun, Cleveland, Ohio, assignor to Shell Oil Company, a corporationof Delaware No Drawing. Original application Dec. 14, 1959, Ser. No.859,128. Divided and this application July 8, 1964, Ser. No. 381,233

7 Claims. (Cl. 260-948) This patent application is a division ofcopending patent application Serial No. 859,128, filed December 14,1959, and which matured as US. Patent 3,161,596 on December 15, 1964.

This invention relates to a new and novel class of oilsoluble phosphonocompounds and particularly to oilsoluble omega-polar substitutedZ-thiaalkylphosphonocontaining compounds.

' The new and novel compounds of the present invention are particularlyuseful in improving liquid hydrocarbons with respect to stability, wearinhibition and extreme pressure properties. These novel compounds havethe general formula:

wherein R is an oil-soluble hydrocarbyl group, such as an alkyl, aryl,aralkyl, alkaryl or cycloalkyl radical having at least 2 and preferablybeing an alkyl radical having from 6 to 18 carbon atoms, R is a C alkylradical or hydrogen, the R s are the same or different groups selectedfrom hydrogen, hydrocarbyl, or cationic groups, such as metallic ornon-metallic cationic groups, such as mono or polyvalent metal or amine,preferably an alkylamine, and the Xs are independently chalcogen atomshaving an atomic number of from 8 to 16, i.e., oxygen or sulfur, and Yis a polar radical such as XR CXXR N(R) where the Xs and R s are thesame as defined above, with preferred polar group being O-H or COOH.Preferred compounds of the general Formula I have the following formula:

O B (II) where Z is a hydroxyl, carboxyl or chloride group.

The Z-thiaalkyl phosphono compounds are prepared by reacting anomega-polar substituted mercaptan having at least 2 carbon atoms with ahalomethylphosphono compound such as chloromethylphosphonic acid or itsester or salt derivative in a suitable solvent, such as an aqueousalcoholic solution, at reflux temperature and under inert conditionsuntil the reaction is completed which normally may require up to aboutdays. The omega-substituted mercapt-ans include omega-substitutedaliphatic mercaptans such as omega-hydroxy, omega-carboxy,omegaaminoethyl, hutyl, hexyl, octyl, decyl, dodecyl, oc-tadecyl,phenyldecyl, benzyl mercaptans and the like.

The following examples illustrate the preparation of the additives foruse in accordance with the present invention.

Example I Stoichiometric amounts of dibutyl chloromethyl phosphonate andbeta-carboxy ethyl mercaptan (HSCH CH COOH) were dispersed in an aqueoussolution of ethyl alcohol 3,235,628 Patented Feb. 15, 1966 ice and KOHand refluxed under a nitrogen atmosphere for about 24 hours. The finalproduct was recovered by acidification and extraction with ether. It wasdibutyl delta-carboxy-Z-thiabutyl phosphonate O 0 04119 HOOCCH2CHzSCH210 0 11 oil-soluble and possessed good extreme pressure and antioxidantproperties.

Example 11 Stoichiometric amounts of monobutyl chloromethyl phosphonateand beta-omega-hydroxy-substituted mercaptan (HSOH CH OH) were reactedunder the conditions of Example I to yield monobutyl omega-hydroxy-Z-thiamethyl phosphonate O 0C4H9 HOCH2CH2SCHro 04H, which possess goodoil-solubility, extreme pressure and anti-oxidant properties.

Example III Di-Z-ethylhexylamine salt of omega-hydroxy-Z-thiabutylphosphonic acid 0 OH-A HOCHgCHgSCHz-;

\OH-A where A is the amine, was prepared by mixing stoichiometricamounts of di-2-ethylhexylamine with the acid at room temperature.

Example IV Monobutyl omega-carboxy decylmercaptornethylphosphonate wasprepared according to the procedure of Example I by reactingstoichiometric amounts of monobutyl chloromethylphosphonate withpotassium salt of omegacarboxydecyl mercaptan.

The following additional compounds were prepared: omegahydroxyoctylmercaptomethylphosphonic acid, omegahydroxydodecylmercaptomethylphosphonic acid, omegaarninohexylmercaptomethylphosphonic acid, dibutyl omegacarboxydecylmercaptomethylphosphonate, phenyl omegacarboxydecylmercaptomethyl acid phosphonate, dithiobutylomega-carboxyhexylmercaptomethylphosphonate, tert-octadecyl amineomega-hydroxydodecyl-mercaptomethylphosphonate and mixtures thereof.

The additives of this invention are novel compounds. They areoil-soluble and can be used in amounts of from about 0.1% to about 25%,preferably from about 0.5% to about 5.0% by weight in various liquidhydrocarbon products, such as natural and synthetic hydrocarbonlubricating oils, greases, fuels (gasoline, kerosene, gas oil, burnerfuel oil), aphalts, waxes, slushing oils, industrial oils, e.g., metalworking and drawing oils, quenching oils, textile oils, hydraulic oils,dielectric compositions and other industrial oils. They are particularlyoutstanding when added in small amounts to lubricating oils andlubricating compositions to impart extreme pressure andantiwearproperties to such materials. Also, these additives are usefuladditives for gasoline, fuel oils, and other light oil products.

The following compositions are illustrative of the invention, thepercentages being by weight, of the indicated additive or additives withthe remainder being essentially the base.

Composition A:

Example Iadditive 2%.

1010 Mineral oil Essentially balance. Composition B:

Example II additive 2%.

1010 Mineral oil Essentially balance. Composition C:

Example IV additive 2%.

1010 Mineral oil Essentially balance. Composition D:

Example II additive 1%.

SAE 90 Mineral oil Essentially balance. Composition E:

Example I additive 2%.

SAE 90 Mineral oil Essentially balance. Composition F:

Example I additive 2% Lauric acid 2%.

SAE 90 Mineral oil Essentially balance. Composition G:

Example I additive 5%.

Ucon 50HB660 (polyethylenepropylene glycol having an SUS viscosity at100 F.

Compositions of this invention were evaluated for their extreme pressureproperties in the 4-Bal1 Wear machine described in Engineering, vol.136, July 13, 1933.

TABLE I.-4-BALL WEAR TEST [1800 r.p.m., sec., steel on steel, ambienttemp.]

Composition: Initial seizure load, kg. Mineral Oil (1010) 40-50Composition A 158-178 Composition B a 158-178 I claim as myinvention: 1. Oil soluble alkylthiarnethylphosphono compound having theformula wherein R is a C -C3 alkyl group, the R s are selectedindependently from the group consisting of hydrogen and C alkyl groupand mixtures thereof, R is selected from the group consisting ofhydrogen and a C alkyl groups, and Y is a polar group selected from thegroup consisting of OH and COOH groups.

2. Omega hydroxy C alkylthiamethylphosphonic acid.

3. Ester of omega-carboxy C alkylthiamethylphosphonic acid and analkanol of from 1 to 4 carbon atoms the acidic groups attached directlyto the phosphorus atom being esterified.

4. Omega carboxy C1048 alkylthiamethylphosphonic acid.

5. Ester of an omega-hydroxy-ZthiabutylphoSphonic acid and an alkanol offrom 1 to 4 carbon atoms.

6. Ester of an omega-carboXy-2-thiabutyl phosphonic acid and an alkanolof from 1 to 4 carbons the acidic groups attached directly to thephosphorus atom being esterified.

7. Dibutyl omega-hydroxy-Z-th-iabutylphosphonate.

References Cited by the Examiner UNITED STATES PATENTS 2,356,754 8/1944Farrington et al. 260-461 XR 2,363,512 11/1944 Far-rington et al.260-461 XR 2,963,505 12/1960 Muhlman et al 260461 3,112,271 11/1963Calhoun 260-461 XR OTHER REFERENCES Abuzov et al., Zhur. Obshchei Khim.,volume 27, pages 2360-2362 (1957).

CHARLES B. PARKER, Primary Examiner.

1. OIL-SOLUBLE ALKYLTHIAMETHYLPHOSPHONO COMPOUND HAVING THE FORMULA